Unsaturated acid esters of hydroxyalkylcarboxyalkylamines and polymers



2,705,228 Patented Mar. 29, 1 955 UNSATURATED ACID ESTERS OF'HYDROXYAL-KYLCARBOXYALKYLAMINES POLYMERS Hilmer E. Winberg, Wilmington, Dell,assignor to E. L du Pont de Nemours and Company, Wilmington, DeL, acorporation of Delaware No Drawing. Application May 15, 1952,

Serial No. 288,023

7 Claims. (Cl. zoo-85.5

This invention relates to polymerizable compounds and more particularlyto those containing a tertiary amino nitrogen and a carboxylic group.

Polymerizable vinylidene compounds. have achieved considerableimportance in recent years for the preparer tion of polymeric compounds.Certain of the polymers have. fiber forming properties and aretechnically important. for textile applications. In general, inertnessunder most conditions is a desirable property. Such inertness isdisplayed by acrylonitrile polymers and, in general, by polyvinylhalides and polyvinylidene halides. This inert-v ness is not however sodesirable when there is question of dyeing the polymer usingconventional dyeing procedures.

This invention has as an object the preparation of new polymerizablemonomeric materials which can be employed in the preparation ofhomopolymers: and copolymers and which contain reactive groups capableof further chemical reaction. A further object is the preparation of newintermediates. Another object is the preparation of new polymers. Otherobjects will appear hereinafter.

These objects are accomplished by the invention of new polymerizabletertiary amines wherein the only. nonaromatic unsaturation is that of avinylidene, CH2=C group linked to one valence of the tertiary aminonitrogen by a group, another valence of the tertiary aminonitrogen beingbonded to a group, -.RsCOOR-2, the third valence being linked either toanother RsCOOR2' group or to a group R5, R3 being an alkylene radicalpreferably of one to three carbons, and R2 and R5 are preferably lower(one to four carbons) alkyl radicals. Particularly useful because oftheir preparability from readily available commercial materials andbecause of the desirable properties of the polymers therefor are thetrialkylamines wherein one of the alkyl groups is of two to threecarbons and has one substituent, a vinylidene COO substituent, and atleast one of the other alkyl groups is substituted by either acarboxylic acid, COOH, group or a salt or ester thereof, thetrialkylamine having only the carboxy and the one vinylidene COOsubstituents.

Compounds of the present invention may be made in various ways, e. g.,by the reaction of an ester forming acrylic compound, i. e., acrylylhalide, with a hydroxy tertiary amine which contains. a carbalkoxygroup. Their polymers, including copolymers, are obtained by subjectingthe monomers to polymerizing conditions in the presence of a freeradical producing catalyst.

The following examples in which parts are by weight are illustrative ofthe invention. 1

EXAMPLE I M ethyl-beta-carbomethoxyelhyl-betamethacrylyloxyethlyamine Toa solution of 112.7 parts of N-methylethanolamine in 120 parts ofmethanol was added portionwise 155 parts of methyl acrylate stabilizedwithphenothiazine. The mixture was cooled to maintain the temperaturebelow 40 C. The solution was then permitted to stand for two days, afterwhich time direct distillation gave 208'parts of colorless productboiling largely at 97 C. under 2.5 of mercury pressure. Onredistillati'onthe .beta-hydroXyethyl-beta-carbomethoxyethylmethylamineboiled at 83? 85 C. under 1 of mercury pressure, 11 1,4505.

Analysis Calculated. for (17111503; 0,, 52.15%; 9.38% 8.69% z l d C,2.45%; S. N, 3 5-8 To a solution of 50 parts of the above tertiary amie, 34.3 parts of triethyl'amine, and 59- partsof dry dioxane cooled tol0-15 C. was slowly added"32.6' parts of freshly distilled methacrylylchloride, maintaining the temperature at l0-20 C. After the addition wascorn.- I

plete, the mixture was warmed to room temperature, stirred for anadditional two hours, then pouredinto 390 P r s of a e The aqu ouslayer. a s tu a d w di m. hl de nd m de sligh l alkal e ith d lutammonium hydroxide. The mixture was then extracted four times with etherand the combined extracts dried over anhydrous magnesium sulfate.After'filtration, the ol t w disti e o v 13 P s oi rude p duc boilingat92-113 C, und r 1.2. 1.6 mm. of mercury pressure. On redistillation,50.6 parts of methyl-betacarbomethoxyethyl-beta-meth-aeryloxyethylamine,boiling at un er 0.2. Qt m rcury p essu e, 1, 1.4544, was obtained.

Analysis cagugaitegcg for c nmom; c. 57.62%; a, 3.35%;

1. .x. .Q' Found: c, 51.97%, H, 8.46%; N. 6.18%.

in: parts of water was added slowly a cold solution of parts of sodiumhydroxide in 500 parts-of water. To the resulting solution was addedslowly 75 parts of propanolamine in 150 parts of water. During thelatter addition, and for two hours thereatter, the solution was s d nd te t mpe atur main ined. b ow 9 At the end of this time, a solution of257 parts of chloride .dihydrate. in 500 parts of hot water wasv addedto the reaction. mixture which was then heated on. a steam bath. foroneshalf hour. The. precipitated barium salt was removed by filtrationand washed with hot Water. Af rv m ryi he lt hiqh i h d 22 P rts wassuspended in 600 parts of water and the suspension was heated to boilingwhile being stirred. The calculated quantity of sulfuric acid was henintroduced gradually from 'a separatory funnel into the well stirredmixture over a period ofabout onehour. Ihe precipitated barium sulfatewas then removed by filtration and the filtrate evaporated to drynessunder vacuum. The white residue of gamma-hydroxypropyliminodiacetic acidwas washed with acetone and dried to give 112 parts of product, M. P.197-l99 C. (dec.).

Analysis Ga llcgigeged for cqnsnos; c, 43.97%; s.ss%; N,

0 Found; c, 43.76%; 6.98%; 7.33%., 1.39%.

A suspension of St) parts of the above acid in '79'IQ-pa'rts of drymethanol was saturated with dry hydrogen chloride while being cooled inan ice bath. After standing .for'zll hours the volatile materials wereremoved from. the clear solution under vacuum. The viscous residue wascovered with anhydrous ether .and dry ammonia was bubbled into themixture while it was being stirred. Afiter saturation, themixturewasfiltered and the filtrate distilled to giue 40.4 parts of dimethylgamma-hydroxypropyliminQ-diacetate as a colorless viscous liquid boilingat 138 C. under 7 mm rcury-p essu e, 1.45 1

Analysis Calcuaged for C9H17NO51- C, 49.30%; H, 7.82%; N,

6.3 Found: C, 49.09%; H, 7.93%; N, 6.24%, 6.30%

According to the procedure of Example I, 18.3 parts of methacrylylchloride was added to a solution of 37.5 parts of the above tertiaryamine and 18.2 parts of triethylamine in 50 parts of dry dioxane. -.Upondistillation of the resultant reaction product 185 parts of dimethylgammamethacrylyloxypropyliminodiacetate, having a boiling point of 140C. under 0.4mm. mercury pressure and a 1.4614, was obtained.

Analysis Ca lrcgaed for CraHzrOsN: C, 54.40%; H, 7.32%; N,

o 0 Fou d: C, 54.70%; H, 7.56%; N, 5.01%

This ester polymerized to a water-white polymer when heated the presenceof iazodiisobutyronitrile for onequarter hour at approximately 90 C.

To a refluxing, vigorously stirred slurry of 73 parts of anhydroussodium carbonate in a solution of 81.8 parts ofbeta,heta-dimethyl-gamma-methylaminopropanol 395 parts of dry methanolwas added slowly 117.2 parts of methyl bromoacetate. The mixture wasstirred under reflux for an additional hour after the addition wascomplete. The mixture was then cooled and filtered and the filtrate wasconcentrated under reduced pressure to remove the methanol. The residualslurry was filtered and the filtrate was distilled to give 82 parts ofmethyl beta,- beta dimethyl gamma hydroxypropylmethylaminoacetate havinga boiling point of 81 C. under 0.1 mm. mer cury pressure and 11 1.4481.

Analysis Calculated for CsHiaOsN: C, 57.20%; H, 10.13%; N,

7.41%; M01. Wt. 189

Found: C, 57.37%; H, 10.37%; N, 7.19%; M01. Wt.

203 (ebullioscopic in CsHs) According to the procedure of Example I,32.6 parts of-methacrylyl chloride was added to a solution of 56.7 partsof the above tertiary amine and 34.3 parts of triethylamine in 100 partsof dry dioxane. Upon distillation of the resultant reaction product 46parts of methyl beta,betadimethylgamma-methacrylyloxypropylmethylaminoacetate, having a boiling point of7682 C. under 0.03 mm. mercury pressure and n 1.4510, was obtained.

- Analysis Calculated for C13H23O4N: C, 60.70%; H, 9.01%; N, 5.44%;Mol.Wt. 257 Found: C, 61.53%; H, 9.38%; N, 5.87%; M01. Wt, 257(ebullioscopic in CsHa) This ester polymerized to a water-white polymerwhen heated in the presence of azodiisobutyronitrile for onequarter hourat approximately 90 C.

EXAMPLE IV- Preparation ofacrylonitrile/methyl-beta-carbomethoxyethyl-beta-methacrylyloxyethylaminecopolymer To a solution of 0.342 part of potassium dihydrogen phosphatein 190 parts water was added sutficient 0.5 N

sodium to give a pH of 7. To the resulting solution was m l ing at leasttwo chain carbon atoms, which nitrogen has solution of the polymer indimethylforrnamide was clear, colorless and strong. It was readily dyedat a pH of 3 with typical acid dyes.

EXAMPLE V Preparation of acrylonitrile/dimethyl gamma-methacrylyljoxypropyliminodiacet ate copolymer To 190 parts of water was added 0.403part of the dimethyl gamma-methacrylyloxypropyliminodiacetate of ExampleII. The pH was adjusted to' 4 with dilute sulfuric acid, then 13 partsof redistilled acrylonitrile, 0.189 part of thiourea and 5.68 parts of3% hydrogen peroxide solution were added and the polymerization waspermitted to proceed under nitrogen for three hours at room temperature.At the end of this time, the precipitated polymer was isolated byfiltration, washed with water, followed by acidified methanol, anddried. There was obtained 8 parts of white polymer of intrinsicviscosity 1.5 (0.2% solution in dimethylformamide at 0.).

Films cast from 15% solutions of the polymer in dimethylformamide werecolorless and tough. They dyed readily at pH 3 with acid dyes and hadgood thermal stability.

The compounds of this invention are polymerizable tertiary amines havingone valence of the tertiary amino nitrogen attached to amethacrylyloxyalkyl or acrylyloxyalkyl group as the only non-aromaticcarbon to car- 1 alkyl.

bon unsaturation in the amine and another valence at tached, by, a chaincontaining at least two chain carbon atoms, to a carboxylic group. Theyhave one and only one vinylidene, CH2= group which is attached to onebalence of a tertiary amino nitrogen by a chain containanother valencebonded through a chain containing at least two chain carbons, to thecarboxyl carbon end of a carboxylic, --C0O, group, generally acarbalkoxyl in which the alkoxyl is of a lower, one to four carbon,

A amines having the tertiary amino nitrogen bonded to an alkyl radicalfurther substituted by a radical, I

wherein n is a cardinal number not greater than one and to at least onealkyl radical having as its only substitution at least one carboxylsubstituent, any remaining valence of said nitrogen being bonded to analkyl radical. These are pictured structurally as of the formula whereinR4 is hydrogen or methyl and Ra is an alkylene radical preferably of oneto three carbons, e. g., methylene, ethylene, propylene; R2 and R5 arepreferably lower (one to four carbon) alkyl radicals; and n is aninteger of one to two. The invention thus includes, in addition to theamines of the examples,N-(beta-dicarbomethoxymethylaminoethyl)methacrylamide andmethyl-betamethacrylyloxyethyl-carboxymethylamine. Alkali metal saltscan also be employed.

The choice of method of preparation of any ethylenically unsaturatedcompound is dependent upon the specific compound. Carbalkoxy containingacrylates can be prepared by reaction of an acrylyl halide, e. g.,acrylyl chloride, with a tertiary amine which contains a reactivehydroxyl group and at least one carboxylic group.

The amines of this invention are polymerizable and copolymerizable. Theyare reactive with reagents which react with ethylenic double bonds. Byvirtue of the tertiary amino group they form quaternary derivatives, e.g.,

by reaction with alkyl halides, alkyl sulfates, or alkyl arylsulfonates. Hydrolysis of the carbalkoxy tertiary amines of thisinvention leads to substantially nonalkaline amino acids, i. e.,generally neutral or acidic. and copolymers of the tertiary amines ofthis invention have superior dyeing properties under conventionalconditions to which textile materials are subject for dyeing with aciddyes. The foregoing detailed description has been given. for clearnessof understanding only and no unnecessary limirations are to beunderstood therefrom. The inventionis not limited to the exact detailsshown and described for preferred class of tertiary amines is the classat Polymers wherein n is a cardinal number not greater than one and toatjleast one alkyl radical having as its only substitution at least onecarboxyl substituent of the class consisting of carboxyl and one to fourcarbon alkyl esters thereof, attached to the alkyl of the amine by thecarboxyl carbo'jn end of said carboxyl substituent, any remainingvalence of said nitrogen being bonded to an alkyl radical.

2. -A tertiary amine having the tertiary amino nitrogen bonded to amethacrylyloxyethyl radical and to at least onefi'alkyl radical havingas its only substitution at least one'iicarboxyl substituent of theclass consisting of carboxyl and one to four carbon alkyl estersthereof, attached to the alkyl of the amine by the carboxyl carbon endof saidi'carboxyl substituent, any remaining valence of said nitrogenbeing bonded to an alkyl radical.

3. ,jA tertiary amine having the tertiary amino nitrogen bonded to amethacrylyloxyethyl radical and to at least one jilkyl radical of one tothree carbons having as its onlyz substitution at least one carboxylsubstituent of the clas'jsjconsisting of carboxyl and one to four carbonalkyl esters thereof, attached to the alkyl of the amine by the carboxylcarbon end of said carboxyl substituent, any remaining valence of saidnitrogen being bonded to an alkyl radical of one to four carbons.

45A polymerizable tertiary amine of the formula wherein x is a cardinalnumber not greater than one, m is; an integer from two to three, n is aninteger from onej to two, y is a cardinal number not greater than four,R1..is a divalent saturated aliphatic hydrocarbon radical of one tothree carbons and R2 is an alkyl radical of one to four carbons.

5. A polymer of a tertiary amine which amine has the formula wherein xis a. cardinal number not greater than one, in is an integer from two tothree, n is an integer from one to, two, y is a cardinal number notgreater than four R1 is a divalent saturated aliphatic hydrocarbonradicaliof one to three carbons, R2 is an alkyl radical of one to fourcarbons.

6. Aicopolymer containing in its composition a major amount: ofacrylonitrile and two to ten per cent of units of a tertiary amine whichamine has the formula H2 H 2)2n x is a cardinal number not greater thanone, m is an integer from two to three, n is an integer from one ,toltwo, y is a cardinal number not greater than four R1 is a divalentsaturated aliphatic hydrocarbon radical'fof one to three carbons, R2 isan alkyl radical 0 Jon 7. A, opolymer containing in its composition amajor amountof acrylonitrile and two to ten per cent of units of atertiary amine which has the tertiary amino nitrogen bondedfto amethacrylyloxyethyl radical and to at least one alltyl radical of one tothree carbons having as its onlysgbstitution at least one carboxylsubstititent of the class consisting of carboxyl and one to four carbonalkyl esters thereof, attached to the alkyl from carboxyl carbon'ipf thecarboxyl substituent, any remaining valence of saidgnitrogen beingbonded to an alkyl radical of one to forth-carbons.

g keferences Cited in the file of this patent

1. A TERTIARY AMINE HAVING THE TERTIARY AMINO NITROGEN BONDED TO AN ALKYL RADICAL FURTHER SUBSTITUTED BY A RADICAL, 